Process for the manufacture of alcohols and ketones



Patented July 1, 1941 UNITED ,STATES. PATENT OFFICE PROCESS FOR. TIiEMANUFACTURE OF ALCOHOL S AND KETONES Benjamin W. Howk, Wilmington, andWilburA. Lazier, New Castle, Del., assignors to E. I. du Pont de Nemours& Company, -Wilmington, DeL, a corporation of Delaware No Drawing.Application August 1 1, 1939, Serial N0. 289,583

20 Claims. (01. 260 593) This invention relates to a catalytic processand more particularly to'a process for the manufacture of ketones andalcohols. More especially the invention relates to the synthesis ofheptadecanone-l and heptadecanol-1 from castor oil.

This application is a continuation-impart of application Serial No.56,084, filed December-24, 1935. In co-pending application Serial No'.56,084,

there is describedadehydrogenation process for the conversion ofoctadecanediol-1,12 to the cor- -responding keto-octadecyl alcohol,which com-' prises heating the glycol'under carefully controlledconditions with a ferrous metal dehydrogenation catalyst. The reactionis conducted so that but slightly more than the theoretical quantityof'hydrogen is evolved fromthe reaction mixture, and the temperatureemployed is maintained below a maximum value of about 240 C. We have nowdiscovered that exhaustive dehydrogenation of primary-secondary glycolsprovides a convenient and practicable method for the preparation ofketones containing one less carbon atom than the original glycol. In

'this process, dehydrogenation of both the primary and secondarycarbinol groups is accompanied by elimination of carbon monoxide, whichreaction is referred to herein as decarbonylation.

Thisinvention has as an object the preparation of ketones fromprimary-secondary glycols. An-.

other object is to provide a catalytic process for preparing ketonesfrom primary-secondary gly- Example I A mixture consisting of 500 partsof technical octadecanediol-L12 and 50 parts of an active nickelcatalyst is charged into a reaction flask equipped with a temperaturemeasuring device, a stirrer, and a gas outlet tube leading to acondenser, appropriate cold traps, and gas meter.

The octadecanediol-Ll2 is melted and the temperature gradually raised,with stirring, to about 185 C., at which temperature vigorous evolutioncols. Still another object is to provide a catalytic process forconverting primary-secondary glycols at least two carbon atomscontiguously between the carbinol groups to ketones containing onelesscarbon atom than the original glycol. A still further object is toprovide a commercially practicable process for preparing ketones fromcompounds having a secondary 'carbinol group separated from a primarycarbinol' group or a group convertible by hydrogenation to a primarycarbinol group by at least two carbon atoms in ebntiguous relation. Afurther object is to provide aprocess for converting castor oilthroughlZ-hydroirystearin to heptadecanone-l. Anotherobject is toconvertcastor' oil through l2 -hydroxystearin to heptadecanol-7.

' A final object is to convert castor oilthrough octadecanediol-1,l2 toheptadecanone-l.

In the preferred embodiment the above objects are accomplished byheating a primary-secondary glycol in which the primary and secondarycarbinol groups are separated by at least two .carbon atoms incontiguous relation a dehydrogena- 1 tion catalyst at atemperatureinexcess of 150 of gas begins. The reaction is continued overa period of 4 to 4.5 hours while raising the temperature graduallyto amaximum in the neighborhood of 270 C. At the end of this period the rateof gas evolution falls oil to essentially zero,

.and the total amount given off corresponds, to

2.67 moles of gas per mole of octadecanediol-1,12 charged to thereaction flask. The reaction mixture is cooled to approximately 150 C.and illtered to separate the catalyst. The catalyst is washed thoroughlywith methanol, the methanol evaporated, and the residue added to themain filtrate. The product is refined by vacuumfractional distillation.There are obtained 53.7 parts of C11 hydrocarbon, B. P. to 143 .C. at 4mm., 323.2 parts of heptadecanone-7, B. P. 159 C. at 4 mm., M. P. 41'C., and 51.1 parts of highboiling residue. The yield of heptadecanone-7is 83.6% of theory based'on the known octadecanediol-1,12 content of thetechnical product employed as starting material; Analysis gave: carbon,80.31; hydrogen, 13.36.

GnHar' requires: carbon 8.0.305 hydrogen, 13.3.8.

Erample II One hundred fifty parts of technical gradeoctadecanediol-l,l2 and 15 parts 'ofan active nickel-on-kieselguhrcatalyst are charged into ,a small high pressurev autoclave. Theautoclave is sealed and hydrogen is forcedlin until the total pressureat room temperature is about 450 and its contents are maintained at atemperature of 250 C. over a period of 7 to 8 hours with vigorousagitation throughout the entire period.

The autoclave is cooled to room temperature and accumulated gasespurged. The reaction product filtered to separate the catalyst andrefined by'vacuum fractional distillation according to the proceduredescribed in Example I. There are obtained 6.9 parts of C11 hydrocarbon,

B. P. 140 to 145 C. at 4 mm., 84.4 parts of,

heptadecanone-7, B. 1?. 163 C. at 6 mm.,-and 14.5 parts of high-boilingresidue. The heptadecanone-7 is essentially free from hydroxylatedproducts, and the amount obtained corresponds ,to a molecular yield of80.7% of theory, based on the pure octadecanediol-L12 content of thetechnical starting material.

Example!!! One hundred fifty parts of technical gradeoctadecanediol-Ll-Z is heated in a small high approximate ratio 1:4. Theyield of ketone-alcohol mixture is 82% of theory, calculated as in-'dicated above in Examples I and II.

/ Example IV 'One hundred fifty parts of ricinoleyl alcohol prepared bythe sodium reduction of castor oil is hydrogenated in a small highpressure autoclave in the presence of 15 parts of active nickel catto500 lbs. per sq. in. Thereafter, the autoclave is obtained 28.4 parts ofC11 hydrocarbon, 7 parts of an intermediate fraction, B. P. 160 to 171C. at 7 mm., 51.8 parts of a C11 ketone fraction, B. P. 171 C. at 7 mm.,and38.1 parts of highboiling residue. The Cu ketone fraction consists ofa mixture of heptadecanone-7 and heptadecenone-7, asindicated byanalysis for iodine number. The presence of saturated ketone in thisproduct is accounted for by the saturation of the for the low gasevolution as compared to that alyst underan initial hydrogen pressure of1500 over a period of about 8 hours.

lbs. per sq. in. The reaction proceeds smoothlyat a temperature of 150to 160 C. and the absorption of hydrogen is complete within a period ofabout30 minutes. At the end of the reaction the hydrogen pressure in thetube is approximately 400 to 500 lbs. per sq. in. Thereafter thereaction vessel and its contents are heated to a temperature of 250 C.andm'aintained at this level The autoclave is cooled and the productsremoved and distilled .under diminished pressure to give 35.1 parts ofC11 hydrocarbon boiling mainly at 140 to 148 C. at 6.5 mm., 66.6 partsof heptadecanone-7, B. P. 169 to '170" at 6.5 mm., and 7.4 parts ofhighboiling residue. The heptadecanone-7 obtained is identical with thatdescribed 'in the foregoing examples.

Example V One hundred fifty parts of rlcinoleyl alcohol and 15 parts ofnickel catalyst are placed in a round-bottomed, three-necked flaskequipped as described in Example I. The reaction mixture is heated withstirring up to a temperature of 232 C. At this temperature a rapidevolution of gas begins and continues over a period of 2.75 hours,during which time the temperature is increased to a maximum of 250 C.The total product is filtered to separate 'the'catalyst and refinedbyyacuum fractional distillatio There obtained with octadecanediol-l,12.

Example VI Two hundred fifty parts of technical gradeoctadecanediol-1,12 and 12.5 parts of a 5% palladium-on-charcoalcatalyst are charged into a reaction flask equipped as shown in ExampleI. The mixture is heated with stirring to a temperature in theneighborhood of 200 to 225 C.,

and in this range the evolution of gas begins at a slow steady rate.Heating is continued over a period of about 11 hours, during'which timethe temperature is gradually raised to a maximum of about 260 C. Thetotal amount of gas evolved is 2.44 moles per mole of octadecanedioltreated. The reaction mixture is cooled, the catalyst separated byfiltration, and the product worked up by vacuum fractional distillation.There are obtained 141.8 parts of heptadecanone-7, B. P. 152

to 154 C. at 3 mm. This corresponds to an 81% conversion, based on theoctadecanediol content of the starting material.

Example VII One hundred fifty parts of octadecanediol-1,12 and 15 partsof nickel-on-kieselguhr catalyst are charged into a high pressureautoclave. The autoclave is sealed and heated at a temperature of 250 C.for a period of 8 hours. At the end of this time the autoclave is cooledto about C. and accumulated gases purged until the internal pressure isapproximately atmospheric. Hydrogen under 1500 lbs. per sq. in. pressureis forced into the autoclave and heating at 150 to C. is continued for 3to 4 hours. During this period hydrogen is absorbed at a steady rate andfresh amolmts are added from time to time in order to maintain the totalpressu-rein excess of about 500 lbs. per sq: in. The autoclave is cooledand the product removed and separated from the catalyst by filtration.Fractional distillation of the filtered product gives 89.2 parts of amain fraction, B, P. 154 to 156 C. at 3 mm., M. -P. 45 C., whichcomprises essentially pure heptadecanal-7. The yield is 85% of theory,calculated on the total amount of pure octadecanediol-1,-l2 in thestarting material. Analysis of the product gave: carbon, 79.71;hydrogen, 13.98.

(5311-1350 requires: carbon, 79.65; hydrogen,

Example VIII Three hundred fifty parts of copper chromite catalyst ismixed with 3500 parts of castor oil temperature of 260 C. underahydrogen-pressure of about 3000 lbs. per sq. in. Under these conditionshydrogen is absorbed rapidly overv a period of 1 to 2 hours. Thereafterthe rate of 81.7 parts of afrac'tion. B. P. 154 to156 C M. P. 45 to 46C., which is identical with the hydrogen'absorptioir slows 'down, and atthe end of 4 hours essentially ceases. During this period fresh hydrogenis admitted at intervals in order to maintain the total pressure in therange of 2500 to 3000 .lbs. per sq. in. When the reduction of both the.double bond and carboxyl group of ricinolein is complete, as indicatedby failure to adsorb further amounts of hydrogen,

the autoclave and its contents are cooled to 250 C., the pressure isreduced to about 500 lbs. per

sq. in., and a small sample of the product removed through the samplingdevice. This material is slurried with 300 parts of nickel-on-kieselguhrcatalyst and the resulting mixture pumped back tered to separate thecatalyst. The filtered product is-refined by vacuum fractionaldistillation in an eiiicient still. There are obtained a main fractioncomprising 1826 parts of heptadecanone 7, B. P. 152 to 154 C. at 3 mm.,which is identical with the heptadeca'none-7 described in the foregoingexamples.

Example IX One hundred fifty parts of castor oil, parts of copperchromite catalyst, and 15 -parts of nickel catalyst are mixed thoroughlyand charged into a small high pressure hydrogenation vessel. Theautoclave and its contents are brought to a temperature of 250 to 260 C.under a'hydrogen pressure of about 3000- lbs. per sq. in. Under theseconditions hydrogen is absorbed and the heating is continued until nofurther absorption of hydrogen indicates complete reduction of thedouble bond and carboxyl group of the castor oil. This requires about 3to 4 hours. At the end of this period the pressure in the autoclave isreduced to about 500 lbs. per sq. in. and the heating is continued at250 C. for an additional 7 to 8 hours... Thereafter the autoclave iscooled further to a temperature of about 150 C. and accumulated gasesremoved by purging down to atmospheric pressure.\' The autoclave is thensubjected toa hydrogen pressure of approximate 1y 1500 lbs. per sq. in.at a temperature of 150 to 175 C. Heating is'continued until no furtherabsorption of hydrogen is noted, which indicates complete hydrogenationof the ketone produced. in previous stages of the reaction. The productis removed from the cooled autoclave. filtered to separate the catalyst,and finally purified by vacuum fractional distillatio'n.- There areobtained heptadecanol-7 described in Example" v11. 1

Although in the foregoing examples we have indicated the use of'certaindefinite conditions of temperature, "pressure, reaction times.catalyst, concentrations of reactants, and the like, it is to beunderstood that these values can be aried somewhat within the scope of.this inventio Broadly speaking, 'our process for converting,

' primary-secondary glycols to ketones'containing one less carbon atomthan the-parent material involves two separate and distinct reactionswhich proceed essentially simultaneously under the 'same conditions overthe same catalyst. The

first reaction is one of dehydrogenation which may proceed in accordancewith the following equation:

RCH(CH:):CH2OH a R-|C|(CH2);CHO

n 1 o The second reaction involves elimination of a molecule of carbonmonoxide from the ketoaldehyde produced by dehydrogenation.

n wnmono R("J(CHz). 1CHa+C0, o o

It is obvious that since both reactions occur under essentially the sameconditions that the aldehyde products may exist only momentarily incontact with the dehydrogenation catalyst.

Generally speaking, the dehydrogenation-decarbonylation process of thisinvention is carried out at temperatures in excess of .about 150 C.

' and preferably atltemperatures in the range of 180. to 265 C. Thereaction can be conducted either at atmospheric. pressure or undersuperatmospheric hydrogen pressures, preferably in the range from 300 to500 lbs. per sq. in.

In the dehydrogenation step there may be used any liquid phasedehydrogenating catalyst which effects liberation of hydrogen fromprimary and secondary carbinol groups in preference to dehydration.These catalysts are metals of group VIII of the periodic tabla and maybe used alone or in various combinations. These catalysts may beusedeither in the form of their oxides or as finely divided metal powderseither in the mas- ,sive state or deposited on suitable porous, easilysuspended supports such as kieselguhr, pumice, and the like. As one ofthe preferred catalysts of the invention might be mentionednickel-onkieselguhr. Catalysts coming within this classification alsofunction as hydrogenation catalysts in the step of converting the ketoneto the alcohol. This reaction may be carried out in situ merely bychanging the conditions to those which favor hydrogenation of the ketonecarbonyl group. For example, a temperature of about 150 to 175 C. andpressure exceeding about 1500 lbs. per scl. in. can be employedconveniently.

The process of this invention is applicable to primary-secondary glycolsin which the primary carbinol group is separated from the secondaryhydrogenation of castor oil or 12'-hydroxystearin,

or the glycols produced by catalytic hydrogenation of other hydroxycarboxylic compounds including 10-hydroxystearin, lo-hydroxypalmitin,

\ and the like.

As pointed out above, an important modification of the process involvesproducing the glycols in situ by catalytic hydrogenation of compoundscontaining a secondary carbinol group separated by at least two carbonatoms in contiguousrelation from another group capable of hydrogenationto aprimary carbinol group. Examples of such compounds are hydroxyacids, hydroxy .glycerides, other. hydroxy esters, or hydroxy aldehydeshaving the hydroxyl group on a carbon other than the terminal carbonatom.v All of these materials are converted in good yields toprimary-secondaryglycols by hydrogenation according to the processesdescribed in U. S. Patents 2,094,611 and 2,079,414. A, lyceride such ascastor oil, for example, may be charged into a hydrogenation autoclaveand treated with hydrogen under pressures up to about 3000 lbs. per sq.in. at temperatures in the neighborhood 01' 250 to 275 C, in thepresence of a copper chromite catalyst. Under these conditions thedouble bond is completely saturated and the carboxyl group undergoesreduction smoothly to a primary carbinol group. In'general, the carboxylreduction catalyst employed in the step of con verting the glyceride tothe lycol has little effect onsubsequent steps of the process. Thedehydrogenation-decarbonylation reaction may be carried out withoutisolating the primarysecondary glycol produced in this manner by addingthe required amount of dehydrogenation catalyst and treating under theconditions described above. Finally, the ketone obtained in thedehydrogenation-decarbonylation step can be conveniently hydrogenated insitu to the corresponding secondary alcohol, using the same catalystemployed in the decarbonylation step.

The process of this invention provides a novel and highly effectivecatalytic method for preparing a wide variety of ketones and alcoholshitherto unknown or unavailable except in small quantities as laboratoryreagents, The process provides a practicable commercial route for thepreparation of heptadecanone-7 and heptadecanol-7 and other ketones oralcohols derivable from naturally occurring raw materials such as castoroil and oiticica oil. The ketones and alcobon other than the terminalcarbon atom under conditions that will convert the ester group to acarbinol group heating theresulting diol while in contact with adehydrogenation catalyst at a temperature in excess of about 150 C.until the evolution of gas ceases, thereby forming a ketone having oneless carbon atom than the diol.

4. The process which comprises heating a primary-secondary glycol havingat least two carbon hols of this invention are of especial interest asintermediates for surface-active agents, wax blending agents and thelike.

.Having described in detail the preferred embodiments of our invention,it is tobe understood that we do not limit ourselves to the specificembodiments thereof except as defined in the following claims.

We claim:

1. The process which comprises catalytically hydrogenating an ester of ahydroxy acid having at least two carbon atoms in contiguous relationbetween the hydroxyl group and the ester group and having the hydroxylgroup attachd to a carbon otherthan the terminal carbon atom underconditions that will convert the ester group to a carbinol group,heating the resulting diol while in contact with a dehydrogenationcatalyst at a temperature in excess of about 150 C. until the evolutionof gas ceases, thereby forming a ketone atoms in contiguous relationbetween the primary and secondary carbinol groups while in contact witha dehydrogenation catalyst at a temperature in excess of about 150 C.

5. The process which comprises heating a primary-secondary glycol havingat least two carbon atoms in contiguous relation between the primary andsecondary carbinol groups while in contact with a dehydrogenationcatalyst at a temperature within the range of 180 to 265 C. until theevolution of hydrogen ceases, thereby forming a ketone having one lesscarbon atom than the primary-secondary glycol.

6. The process which comprises heating a primary secondary glycol havingat least two carbon items in contiguous relation between the primary andsecondary carbinol groups while in contact with a'dehydrogenationcatalyst at a temperature in excess of about .150" C. until theevolution of gas ceases? thereby forming a ketone having one less carbonatom than the diol and then catalytically hydrogenating the ketone tothe corresponding alcohol.

'7. The process which comprises catalytically hydrogenating castor oilunder conditions that will conv' t the ester radical contained thereinto a carb..iol group and saturate the ethylenic double bond, heating theresulting octadecanediol-1,12 while in contact with a dehydrogenationcatalyst at a temperature in excess of about 150 C. Until the evolutionof gas ceases, thereby forming heptadecanone-7, and then catalyticallyhydrogenating the heptadecanonefl to heptadecanol-7.

8. The process which comprises catalytically hydrogenating castor oilunder conditions that will convert the ester radical contained thereinto a'carbinol group, heating the resulting diol while in contact with adehydrogenation catalyst at a temperature in excess of about 150 C.until the evolution of gas ceases, thereby forming heptadecanone-7.

having one less carbon atom than the diol and then catalyticallyhydrogenating the ketone to the corresponding alcohol.

2. The process which comprises catalytically hydrogenating an ester of ahydroxy acid having at least two carbon atoms in contiguous relationbetween the hydroxyl group and the ester group and having the hydroxylgroup attached to a .carbon other than the terminal carbon atom underconditions that will convert the ester group to a carbinol group,continuing the hydrogenation in order to saturate any unsaturatedcarbonto-carbon linkages, heating the resulting diol while in contactwith a dehydrogenation catalyst at a'temperature in excess of about 150C. until the evolution of gas ceases, thereby forming a ketone havingone less carbon atom than the diol and then catalytically hydrogenatingthe ketone to the corresponding alcohol.

3. The process which comprises catalyticallyhydrogenating an ester of ahydroxy acid having at least two carbon atomsin contiguous relationbetween the hydroxyl group and the ester group and having the hydroxylgroup attached to apar- 9. The process which comprises heatingoctadecanediol-1,12 while in contact with a dehydrogenation catalyst ata temperature in excess of about 150 C.

10. The process which comprises heating octadecanediol-1,12 while incontact with a dehydrogenation catalyst at a temperature within therange of 180 to 265 C. until the evolution of gas ceases, therebyforming heptadecanone-7.

11. The process which comprises heating octadecanediol-1,12 while incontact with a dehydrogenation catalyst at a temperature in excess I ofabout 150 C. until the evolution of gas ceases,

7 characterized catalyst contains as an active catalytic component ametal of group VIII of the periodic table.

16. The process in accordance with claim 1 characterized .in that thedehydrogenation catalyst contains nickel as an active catalyticcompound. V

17. The process in accordance with claim 1 in that the dehydrogenationcatalyst contains palladium as an active catalytic component. 7

18. The process in accordance with claim 5 characterized in that thedehydrogenation catalyst contains as an active catalytic component ametal of group VIII of the periodic table.

19. The process in-accordance with claim -5 characterized in that thedehydrogenation catalyst contains nickel as an'active catalyticcomponent.

20. The process in accordance with claim 5 characterized in that thedehydrogenation catalyst contains palladium as an active catalytic i0component.

BENJAMIN w. HQWK. WILBUR A. LAZIER.

CERTIFICA'I'EOF CORREC'IQIYONQ Patent No. 2,2h7,756. July 1, 19in.

BENJAMIN w. HOWK, ET AL.

-lt is herebiy certified that error appears in the printed specificationof the above numbered patent requiring correction as followsi Page 1,second ooluynn, line-14.7, for "01 331 read --C H 0--; page 14, secozficolumn, line 25, claim 6, for theword"'items" read -atoms--';line 1+0,claim 7,

for "150 C.v Until" readv "150 C. until--; page 5:, first co1umn,'line 15-6,. claim 16, for "'oompotndf read --component--; and that the said'Letter s Patent should be read with this correction therein that thesame m y conform to the record of the case in the Patent Office. I

Signed and sealed'tnis 5th day of August, A.- n. 19in.

- Henry Van Arsdale,

(Seal) 4 Act'ing Commissioner of Patents.

